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International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com Extraction and Characterization of Lignin from Moroccan Sugarcane Using Response Surface Design S. Aoul-hrouz a,*, Y. Essamellali a,b, M. Zahouily,a,b a Laboratory of Materials, and Valorization of Natural Ressources (URAC 24), Faculty of Sciences and Technical Mohammedia, Hassan II University of Casablanca, Morocco. b MAScIR Foundation, VARENA Center, Rabat Design, Madinat Al Irfane, 10100 Rabat, Morocco

Abstract— The central composite design was used to design an agar to produce tableware packaging material ; iv) sugarcane experimental program to provide data to model the effects of bagasse ash and cane ash can partially replace various factors on extraction lignin from Moroccan sugarcane cement and act as pozzolanic additive in manufacturing of bagasse. The variables chosen were volume, and ash block; v) Sugarcane bagasse ash mixed with temperature, and reaction time. The mathematical relationship Arabic gum and water to produce ceramic and refractory of extraction yield on the three significant independent products ; and vi) Both sugar cane combined and their mixture variables can be approximated by a nonlinear polynomial with are used with phenol formaldehyde resin and model. Predicted values were found to be in good agreement wax to manufacture composite board. with experimental values. This procedure provides several Lignin is an amorphous, and consists in a complex phenolic advantages such as high yield, clean isolated lignin, and short composed of three phenylpropane monomeric building reaction time. This lignin was submitted to a comprehensive units [7-10]. The type of monomeric units present in lignin structural characterization employing spectroscopic (UV, FTIR, structure and their relative abundance depend on its botanic liquid state 13C NMR and MALDI ToF spectroscopy) and origin. The major chemical functional groups present in lignin different complementary analysis such as scanning electron structure include hydroxyl, methoxyl, carbonyl and carboxyl microscope (SEM), thermogravinometric analysis (TGA) and moieties in various amounts depending on its botanic origin derivative thermogravinometric (DTG). Results obtained [11]. Hydroxyl groups and free positions in the aromatic ring showed that this lignin is mainly composed of G and S units are the most characteristic functions in lignin, which determine and less free hydroxyls and highlights the absence of residual its reactivity and constitute the reactive sites to be exploited in in lignin. macromolecular chemistry. Keywords—Lignin; Bagasse; Moroccan sugarcane; Response Lignin has been studied for two general uses; the first is Optimization; Central Composite Design. production of small molecule chemicals by or I. INTRODUCTION refinery process. Catalytic methods used to convert lignin include various types of reduction, oxidation, and catalytic Sugarcane bagasse, Saccharumofficinarum L., is one of the cracking process [12-14]. Because lignin is an aromatic largest residuals on agriculture in the world [1-3]. This fibrous derived from , this is an ideal strategy to residue is obtained after crushing and extraction of juice from substitute -based feedstock by those based on the sugarcane. Sugarcane is an energy crop that is largely renewable resources. However, additional research is needed to grown on flat land in countries such as Brazil, China, India, overcome serious practical issues associated with the huge Thailand and Australia [4]. In Morocco, the production of sugar energy costs and necessary purification process to produce cane performed in 2013 is of the order of 580000 tonnes against small molecule chemicals from this complex natural material. 510834 tonnes in 2012, an improvement of 13%. In general, 1 The second approach to the general use of lignin is as a starting tonne of sugarcane generates 280 kg of bagasse; thus, with one material of a diversity of commercial polymer products [15, production of about 580000 tonnesof sugarcane, Moroccan 16]. The incorporation of lignin into polymeric materials produced 162400 tonnes of bagasse during the year 2013 [5]. directly or after chemical modification, is recognized as one of Normally sugarcane bagasse has been used as a fuel to generate the most viable approaches to accomplish its valorization and power of sugar mill. However, a huge quantity of the remaining properly exploit its unique intrinsic properties [17, 18]. bagasse is not used and burnt in the fields, which can cause However, the physicochemical properties of lignin, and environmental problems. Sugarcane bagasse is a rather therefore its suitability for specific polymer applications, are heterogeneous material, generally consisting of three main largely dependent on the species and the isolation components: 50% and 25% each of processes [19]. The applications of material from lignin that and lignin [6]. have been identified include packaging films, food coatings, Because of its low ash content, bagasse offers numerous cationic , hydrogels and biomedical uses. Recently, advantages for usage in bioconversion processes using lignin extracted from herbaceous plants are currently receiving microbial cultures. Also, in comparison to other agricultural increasing attention as proven by the recent industrial and pilot residues, bagasse can be considered as a rich solar energy scale production of nonwood lignin by Green Value SA and reservoir due to its high yields (about 80 tonnes per hectare in CIMV, respectively [20, 21]. The reasons justifying this recent comparison to about 1, 2 and 20 tonnes per hectare for wheat, interest stand in the annual renewability of herbaceous plants, other grasses and , respectively) and annual regeneration their high tonnage per year, the increased conversion of capacity [1]. cellulosic substrate into biofuel when lignin is first extracted from the lignocellulosic feedstock, and the improved Sugarcane bagasse wastes have been applied in the following economics of cellulosic processes when developing value- instances: i) cellulose, lignin, rind, comrind, pith enhance added lignin co products. However, the physicochemical reinforcement in materials manufactured based on different properties of lignin, and therefore its suitability for specific methods applied; ii) Mixed with tapioca and glycerol to polymer applications, are largely dependent on the plant species produce composite materials; iii) mixed with gelatin, starch and and the isolation processes [19]. The resulting increased IJTRD | Jan-Feb 2017 Available [email protected] 185 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com heterogeneity and complexity of herbaceous lignin compared to order to allow the estimation of pure error)] were carried out lignin and the much more limited knowledge of their and the total number of experiments were calculated from the chemistry requires that additional efforts be dedicated to their following equation 1 [26] : characterization [22-24]. n N =2 + 2n + nc (1) Therefore, in the present study, the extraction of lignin present Where: N is the total number of experiments required; n is the in the Moroccan sugarcane bagasse was optimized using the number of factors; and c is the number of center points. central composite experimental design, by studying three factors: the amount of sodium hydroxide, temperature, and In this study, the response was lignin extraction yield (Y%). reaction time, aiming at extracting lignin in a highly efficient Each response was used to develop an empirical model that way. The structure of the extracted lignin was characterized correlated the response to the quantitative experimental with Fourier transform infrared spectroscopy (FTIR), 13C variables or factors for lignin extraction, using a second-degree nuclear magnetic resonance (13C NMR), UV-visible polynomial equation as given by equation 2: spectroscopy, thermogravimetric analysis (TGA) and derivative Ŷ = β0 + β1X1 + β2X2 + β3X3 + β12X1X2 + β13X1X3 +β23X2X3 + thermogravinometric (DTG). 2 2 2 β11X1 + β22X2 + β33X3 (2) II. EXPERIMENTAL Where β0 the constant coefficient, βi the linear coefficients, βij A. Raw naterials the cross-product coefficients and βii is the quadratic coefficients. The software JMP.7 was use d for the experimental Sugarcane bagasse was obtained from a local supplier design, data analysis, model building, and graph plotting. (COSUMAR is a Moroccan group, a subsidiary of the National Investment Company, specializing in the extraction, refining III. RESULTS AND DISCUSSION and packaging of sugar in different forms. It is the only Moroccan sugar bowl operator). A. Experimental Design Preliminary experiments were carried out to screen the B. Extraction process appropriate parameters and to determine the experimental The method of separation of lignin is an alkali treatment which domain. From these experiments, the effects of three variables consists to hydrolyze bagasse (5%) by hot water 60°C for a sodium hydroxide weight (X1), temperature (X2) and reaction period of 120 minutes in order to remove hemicelluloses. The time (X3) are investigated on lignin extraction yield as residue obtained is treated with sodium hydroxide (NaOH response. The experimental design matrix and the 15%). Then, the is recovered acidified with 5N corresponding experimental parameters and response value sulfuric acid H2SO4 to pH between 2 and 3. The precipitate were shown in table 2. formed is washed, air dried, and then crushed in a mortar to The sign and value of the quantitative effect represent tendency obtain a uniform powder. and magnitude of the term’s influence on the response, C. Method of experimentally design respectively. A negative sign in front of the terms indicates the antagonistic effect; whereas the positive sign shows the The central composite design (CCD) is an experimental design synergistic effect. The quality of the model developed was used to achieve maximal information about a process from a evaluated based on the correlation coefficient value. The R minimal number of experiments [25]. For k independent value for equation 3 was 0.9855. The R value obtained was variables was employed to design the experiments in which the relatively high, indicating that there was a good agreement variance of the predicted response, Ŷ, at some points of between the experimental and the predicted values from the independent variables, X, is only a function of the distance model. The R2 value for equation 3 was 0.9714. This indicated from the point to the design center. In CCD, the central that 97% of the total variation in the extraction yield was composite face centered (CCFC) experimental design was used attributed to the experimental variables studied. From the in this study to determine the optimal conditions and study the statistical results obtained, it was shown that the above model effect of three variables. Sodium hydroxide weight (X ), 1 was adequate to predict the extraction yield within the range of temperature (X ) and reaction time (X ) are investigated as 2 3 variables studied. independent variables and extraction yield as response. After selection of independent variables and their ranges, The final empirical model in term of coded factors after experiments were established based on a CCFC design with excluding the insignificant terms for extraction yield (Y %) is three factors at three levels coded as -1, 0 and +1. The coded shown in equation 3 : and uncoded independent variables used in this study are listed in table 1. Y% = 0.27 (± 0.004) + 0.03 (± 0.003) X1+ 0.04 (± 0.003) X2 - 0.006 (± 0.003) X3 - 0.03 (± 0.003) X2X3 + 0.03 2 Table 1: Experimental ranges of the independent variables used (± 0.005) X2 - 0.09 (± 0.005) X3 (3) in the central composite face centered design for the lignin The measured responses can be plotted based on the responses extraction yield (Y%) calculated by the model. For this, it is necessary to plot the Factors Codes Levels adequacy of the model. The plot of experimental and predicted values of extraction yield (Fig. 1) from multiple linear -1 0 +1 regressions showed a good fitting function. Volume of NaOH (ml) X1 15 25 35 Table 2: Central composite face centered experimental design Temperature (°C) X2 25 62.5 100 matrix of factors (X) and the response (Y) of lignin extraction yield (%). Reaction time (min) X3 30 75 120 Observed yield Run order X1 X2 X3 In this study, a total of 16 experiments [consisting of 8 factorial (%) points, six star points and four replicates at the center points (in 1 -1 -1 -1 14.49 IJTRD | Jan-Feb 2017 Available [email protected] 186 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com 2 1 -1 -1 15.16 Table 3: Summary of ANOVA results of lignin extraction yield 3 -1 1 -1 27.92 (Y%) 4 1 1 -1 34.87 Coefficie Sun of Mean P-value 5 -1 -1 1 14.45 Term F-value nt squares square * 6 1 -1 1 24.81 0.0000 7 -1 1 1 19.73 - 8 8 1 1 1 27.70 0.0113 <0.001 0.0000 - 9 0 0 0 27.82 6 * 0.27508 3 33.486 10 0 0 0 28.11 0.0220 0.0012 β 0.03371 0.0000 3 11 1 0 0 31.91 0 6 * β 0.046965 3 64.997 12 -1 0 0 24.16 1 0.0004 0.0002 β -0.00641 0.0000 8 13 0 1 0 33.78 2 1 * β - 3 1.2108 14 0 -1 0 28.12 3 0.0078 0.3143 β 0.031219 0.0000 22.975 15 0 0 1 17.10 23 0 0.0030 β 0.037450 4 8 16 0 0 -1 17.76 22 0.0037 * β 9 0.0001 10.896 33 0 0.0164 Residu - 3 3 0.0251 * e 0.097724 0.0001 74.192 8 0.0001 Total - 3 3 0.0020 * - 0.0003 - 4 - 4 - 0.0725 - 0.0008 4 2 * P-value < 0.05: significant Figure 3: Shows the interaction between temperature (X2) and reaction time (X3) at constant value of the sodium hydroxide Figure 1: The predicted vs observed plot for lignin extraction volume X1 = 0 (Fig. 3a), and the interaction between sodium yield (Y%) hydroxide volume (X1) and reaction time (X3) at constant value of température X2 = 0 (Fig. 3b). The ANOVA required to test the significance and adequacy of the model is listed in Table 3. From this ANOVA, the model F- value of 22.9259 implied that the model was significant. Values of "probability > F" (is worth 0.0006) less than 0.05. In this 2 case, the linear terms (X1, X2 and X3), the squared terms (X2 2 and X3 ) and the interaction term (X2X3) were significant model terms. The relationship between the response and experimental variables can be illustrated graphically by plotting the response values from the levels of variables simultaneously. The topography of the response surfaces in three dimensions can also be illustrated by lines isoresponse outline, which shows Fig. 1. Response surface plot of lignin extraction yield (y) as curves of constant response of a twovariables. These plots were function of temperature (X2) and reaction time (X3) at X1=25 useful for studying the effects of changes in the factors studied ml (Fig. 3a), and as function of sodium hydroxyde volume (X1) in the field and, therefore, to determine the optimal and reaction time (X3) at X2 = 62.5 °C (Fig. 3b). experimental conditions. Fig. 2 shows the interaction between sodium hydroxide volume (X1) and temperature (X2) at The investigation of the theoretical model representing the constant value of the reaction time X3 = +1 (Fig. 2a) and X3 = - polynomial regression of the extraction efficiency of lignin 1 (Fig. 2b). showed that if X1 = 25 ml, X2 = 97 °C and X3 = 75 min; the value predict from the results using response surface model is 35%. The experimental checking in this point, i.e. under the optimum reaction conditions such as: sodium hydroxide volume = 30 ml, temperature = 25 °C and reaction time = 67 min with high lignin extraction yield 27%, confirms this result. Lignin offer potential for several applications in the field of biomaterials [20, 21]. They can, for instance, be used as green components in thermoplastics or as reagents in polyurethanes, polyesters, phenolic and epoxy resins. However, each application requires that the lignin have specific structural characteristics and levels of purity. Figure 2: Response surface plot for the lignin extraction yield (Y) as function of sodium hydroxyde volume (X1) and The chemical composition of sugarcane bagasse in the as temperature (X2) at a fixed reaction time of X3 = 120 min (Fig. received condition along with that reported in the literature is 2a) and 30 min (Fig. 2b). shown in Table 4. The analyses were performed and the reported values are expressed in relation to the dry weight of raw bagasse. It can be seen that the lignin content (27 %) obtained in the present study is comparable than that reported by others for these type of from Brazil and China [27, 28]. The other constituents are somewhat comparable giving IJTRD | Jan-Feb 2017 Available [email protected] 187 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com the total mass balance of 99.5%. Density values of sugarcane C = O ester carbonyl band to 1751 cm-1. The two strong bands bagasse and extracted lignin were found to be 1.25 and 1.75 at 1230 cm-1 and 1074 cm-1 correspond to C-O bonds aromatic kg.m-3 respectively. High-density value in extracted lignin can and aliphatic esters. be explained by the elimination of cellulose and . c. 13C NMR spectrometry Table 4: Comparison of chemical composition sugarcane 13C NMR spectrometry has frequently been used in lignin bagasse of Moroccan with Brazil and China. structural studies at qualitative and quantitative levels. 13C NMR spectra of bagasse lignin and lignin acetate were illustrated in Fig. 5. In order to illustrate the distinct attributions, the corresponding assignments identified for the lignin are listed in Figure 6 according to the previous literatures [32, 33].

B. Charaterization of extracted lignin a. Lignin acetylation Lignin acetylation was carried out according to the published method [29], this lignin sample (≈ 200 mg) was acetylated with 2-4 ml of acetic anhydride/pyridine (1:1, v/v) at room temperature overnight in a 100-ml flask. Ethanol (50 ml) was added and, after 30 min, the solvents were removed using rotary evaporation. Repeated addition and removal (rotary Figure 4: FT-IR absorption spectra of (a) lignin isolated from evaporation) of ethanol (five times) resulted in the removal of Moroccan sugarcane bagasse and (b) lignin acetate sugarcane acetic acid and pyridine from the sample. The precipitated The near absence of typical signals between 90 lignin acetate was collected after centrifugation and dried under 13 high vacuum for 24 h (> 75% recovery yield). and 100 ppm in the C NMR spectrum of lignin confirms the absence content of associated in lignin. In b. Chemical structure by FTIR analysis aliphatic region below 102 ppm, signals at 75.99, 74.47, 73.14 The Temperature Programmed Reduction (TPR) of AlP and and 63.66 ppm are attributed to β-O-4’ linkage, which is shown the most abundant linkage in lignin fractions. After acylation, SiP calcined at 400°C does not present any hydrogen the signals centered at 169, 130 and 102 ppm are attributed to consumption indicating that AlP and SiP are irreducible in the the aromatic acetyl, C1 in syringyl β-O-4 and CH in acetyl range of temperature studied. On the other hand, the TPR 3 spectra of MoAlP and MoSiP shown in Fig. 5, revealed that, at group, respectively. This observation is in agreement with the temperatures higher to 500°C, three reduction peaks. The results found with the FT-IR spectra, confirming the absence of bands characteristic of the cellulose. consumption of hydrogen of the MoAlP and MoSiP are summarized in Table 4. d. Scanning electron micrgraph (SEM) The specter FT-IR of lignin isolated from sugarcane bagasse is The morphology of the surface was observed in scanning presented in Fig. 4. The absorption peak at ≈ 3426 cm-1 electron micrograph (SEM) images of extracted lignin in belonged to the stretching of O-H groups, inclusive of R-OH comparison with Moroccan sugarcane bagasse (Fig. 6). It and Ar-OH. Peaks appear at 2916 cm-1 may be attributed to the clearly appears that some modifications have taken place after C-H stretching in the lignin molecules. Aromatic skeletal alkali treatment. Fig. 6a shows that the fibers of bagasse were vibration bands (1597, 1512, and 1490 cm-1), ring breathing covered by lignin and hemicellulose thereby forming a complex bands (1365 and 1329 cm-1), and aromatic C-H deformation three-dimensional structure. The analysis of the obtained bands can be seen for the lignin isolated from Moroccan picture from lignin (Fig. 6b) shows clearly a homogeneous sugarcane. In particular, all bands characteristic of G units are microstructure made up of layers of various sizes and forms. found markedly stronger (1512, 1256, and 1060 cm-1), This confirmed the removal of major parts of cellulose and indicative of a predominance of G units in this lignin. At 1033 hemicellulose after alkaline treatment. cm-1, the band mainly accounts for the C–H in-plane deformation in syringyl unit. The presence of syringyl (S) and e. Thermal stability guaiacyl (G) bands with absence of the band of hydroxyl Thermal stability of the bagasse and pure lignin derived from -1 phenyl propane (H) at 1166 cm in the spectra for lignin, bagasse (after removal of cellulose and hemicelluloses) were indicate that the lignin extracted from Moroccan sugar cane investigated by the thermogravinometric method. bagasse is more similar to wood lignin than annual plant lignin, Thermogravinometric analysis (TGA) and first derivative which is normally HGS lignin [30]. Furthermore, the thermogravinometric (DTG) curves are presented in Fig. 7. -1 absorption band observed at ≈1490 cm confirms that lignin TGA curves reveal the weight loss of substances in relation to polymer does not change significantly during the soda the temperature of thermal degradation, while the first extraction procedure [31]. After acylation, lignin becomes derivative of that curve (DTG) shows the corresponding rate of soluble in many organic solvents such as dichloromethane, weight loss. The maximum rate of degradation of bagasse was acetone, THF, 1, 4-dioxane, DMSO. The spectrum of the observed at around 320 °C (Fig. 7a) while that the rate of acetylated lignin clearly shows the complete disappearance of degradation of the lignin derived from bagasse becoming -1 the hydroxyl functions at 3490 cm and the appearance of the maximum at around 280°C (Fig. 7b). The thermal

IJTRD | Jan-Feb 2017 Available [email protected] 188 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com decomposition of lignin results from complex reactions, which saturation of aromatic rings rupture of lignin C-C bonds, CO2, explains the various hypotheses found in literature [34]. The CO and gives structural rearrangements [37]. results (Figure 7a) of the thermogravimetric analysis showed f. UV-visible spectroscopy and MALDI-ToF that the first weight loss step occurs at ≈ 40 to 150 °C due to the moisture of the sample and evaporation of absorbed water, UV-visible absorption measurements of lignin isolated from subsequently the second stage occurred at around 250 to 300 °C bagasse was carried out using sodium hydroxide (1%) aqueous could be ascribed to the degradation of solution. This solution dissolves the lignin. Spectra of lignin components of the lignin. monoxide, carbon dioxide and raw bagass are shown in Fig. 8. Lignin shows absorption and methane are also formed [35]. Decomposition of aromatic maxima at 280 nm [38]. rings occurs around 400 °C [36]. Continuous heating leads to

Figure 5: 13C NMR spectra of the (a) lignin isolated from Moroccan sugarcane bagasse and (b) acetylated lignin

Figure 6: SEM images of (a) raw bagasse and (b) lignin isolated from bagasse. MALDI-ToF is a soft ionization technique to obtain fragments of high molecular weight (m/z). The MALDI-ToF spectrum were performed to analyze the obtained lignin and have an information about it structure (Fig. 9). For analysis the lignin, the samples were derivatized by acetylation. The lignin acetate sample must be previously dissolved in an organic solvent and then crystallized in a matrix. From a wide range of available matrices is in the 2, 5-dihydroxybenzoic we observed the most fragments derived from the lignin acetate. The analysis was performed in positive mode. A sample of lignin acetate was solubilized in MALDI-ToF analysis in positive mode of the non-acetylated lignin suggested that the structure of lignin was too fragile to get mass fragments greater than m/z = 900 [39]. In our conditions, we observed on the MALDI-TOF spectrum of acetylated lignin fragments with mass (m/z) equal to 1325 (Fig. 9). Its abundance is low. The improvement of the solubility of the lignin by acylation yielded a mass fragment (m/z) of greater than 900 [40]. This observation agrees with the results of the FTIR spectra, which indicate that the lignin extracted from Moroccan sugar cane bagasse is more similar to wood lignin than annual plant lignin.

IJTRD | Jan-Feb 2017 Available [email protected] 189 International Journal of Trend in Research and Development, Volume 4(1), ISSN: 2394-9333 www.ijtrd.com CONCLUSION Central composite face-centered design was successfully employed to optimize the extraction process of lignin from Moroccan sugarcane bagasse. The results showed that three variables; extraction temperature, sodium hydroxyde volume and reaction time have significant effect on lignin extraction yield. The model established for this purpose explains up to 97% of the variance and thus adequately predicted the lignin extraction yield within the range of variables studied. On the optimum extraction condition, obtained from the results using response surface methodology, the lignin extraction yiel was 35%. FT-IR spectroscopy, 13C NMR spectrometry and MALDI-ToF spectroscopy characterization of the lignin Figure 7: TGA and DTG curves of raw bagasse and lignin confirm that all the cellulose and hemicelluloses were (recorded in air atmosphere). eliminated during the separation process and reveals that lignin is mainly composed of G and S units and less free hydroxyls and highlights the absence of residual sugars in lignin. Furthermore, the lignin was analyzed by different complementary analysis such as scanning electron microscope, UV-visible spectroscopy, thermogravinometric analysis (TGA) and derivative thermogravinometric (DTG). References [1] A. Pandey, C.R. Soccol, P. Nigam, V.T. Soccol, 2000. Biotechnological potential of agro-industrial residues. I: sugarcane bagasse. Bioresource Technology, 74, 69-80. [2] D.R. Mulinari, H.J.C. Voorwald, M. Cioffi, M. Silva, Figure 8: UV-Vis absorption spectra of raw bagasse and T.G.D. Cruz, C. Saron, 2009. Sugarcane bagasse lignin. (a) Lignin powder, (b) Sugarcane bagasse wastes and cellulose/HDPE composites obtained by extrusion. (c) lignin in sodium hydroxide (1%) aqueous solution Composites Science and Technology, 69, 214-9. [3] J.M. Hernández-Salas, M.S. Villa-Ramírez, N.J.S. Veloz- Rendó, K.N. Rivera-Hernández, R.A. González-César, M.A. Plascencia-Espinosa, 2009. Comparative hydrolysis and fermentation of sugarcane and agave bagasse. Bioresource Technology, 100, 1238-1245. [4] K. Hofsetz, M. A. Silva, 2012. Brazilian sugarcane bagasse: Energy and non-energy consumption. and Bioenergy, 46, 564-573. [5] Cosumar Group is a leading upstream sugar aggregator and contributes to the development of sugar sector with a total dedicated areas of 90 000 ha over 5 regions from Morocco: Doukkala, Gharb, Loukkos, Tadla, Moulouya. 80,000 farmers who work on producing and sugar cane that represents 10 million wordk days a year.

Figure 9: MALDI-ToF spectrum of lignin acetate derived w.ww.cosumar.co.ma. from Moroccan sugarcane bagasse [6] D. Fengel, G. Wegener, 1989. Wood: Chemistry, ultrastructure, reactions. New York: Walter de Gruyter. Based on the results of the FTIR analysis, 13C NMR and [7] M. Ayyachamy, F.E. Cliffe, J.M. Coyne, J. Collier, M.G. MALDI-TOF we proposed certain chemical structures of Tuohy, 2013. Lignin: untapped biopolymers in biomass polymer fragments from the Moroccan lignin bagasse conversion technologies. Biomass Conversion and (Fig.10). , 3, 255-269. [8] S. Sarkar, B. Adhikari, 2001. Synthesis and characterization of lignin-HTPB copolyurethane. European Polymer Journal, 37 (7), 1391-1401. [9] R.W. Thring, P. Ni, S.M. Aharoni, 2004. Molecular weight effects of the soft segment on the ultimate properties of lignin-based. International Journal of Polymeric Materials, 53, 507-524. [10] C.A. Cateto, M.F. Barreiro, A.E. Rodrigues, 2008. Monitoring of lignin-based polyurethane synthesis by FTIR-ATR. Industrial Crops and Products, 27 (2), 168- 174. [11] K.V. Sarkanen, H.L. Hergert, 1971. Classification and distribution, in: K.V. Sarkanen, C.H. Ludwig (Eds.), Figure 10: Chemicals structures of the Moroccan lignin bagasse polymeric fragments.

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Production of activated carbonfrom Luscar char: experimental and modeling

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